Sulfurized tall oil-containing compositions



Patented Mar. 10, 1953 -SULFIJ'RIZED TALL OIL-CONTAINING COMPOSITION 8-,

Stanley PJWaugIifWestfield, N. J'.,, assignor to Title Water Associated Oil' Company, Bayonne, N'.'J'., a' corporation-of Delaware N:Drawing., Application June 2', .1949,

\ Serial No. 96331 Thepresent inventionrelates to. novel compositions, adaptablefor use ascutting oils, andpreparationthereof.

As is known by those skilled in the. art, the presence of sulfur in cutting oilsis highly desirable and, particularly, for the reason that. sulfurized oils retain their lubricating and cutting qualities better than unsulf-urized oilspduringcuh tingoperations. However, oils vary greatly in their.ability to absorb and maintain'sulfurein stable solution and/or combination andmanyloils do not possess thecapacity of absorbing, and maintaining: in stable solution and/for combination, a. concentration of sulfur suflicient to per.- formin ahighly satisfactory manner as cutting oils, particularly for use in-heavy duty cutting operations. Hence, and asevidenced-by the numerous investigationsthat .havebeenmade and, on the. basis of, which manypatents have. issued, the art has resorted-to use of sulfurized basesfor addition to mineral oils toprovide cutting oil compositions. For such, purposes, the bases employed are normally characterized by having a highnsulfur absorption capacity, e. g., a. greater capacity for absorbing sulfur, than the oilof lubricating quality with which the sulfurized. baselis blended-to form cutting oilcompositions.

Qne type of such bases whichqha-slfound considerable application as a sulfurized= cuttingoil base is tall oil, a productwell-lmown to the art, obtained as a lay-product: paper. manufacturing. Tall oil has-a high sulfur absorption capac! ity and, forthat;- reason, as well asfor purposes .of economy, has considerable merit for such usage. In illustration. thereof reference is made to, suliurizedtall oil-containing cutting oils asidisclosed in patents such as; U.. S. Patent No. 2,198,562, No; 2,417,283 and No. 2,492,193.

Tall oil, either incrude-or refined: form, ischaracterized by containing fatty acids, rosin acids, and sterols. Depending upon the particular source from which the tall oil isobtained, and :whether in crude or refined form, therproportions of the aforesaid constituents intall oil may-vary over. a rather-wide range For example, in some instances; the fatty acid content may vary-between aboutZO to about 60%, therosin-acids from about-7O to about with theremainderbeing sterols'. A more specific-illustration includes a commercially available talloil composition marketed: asIndusoil: A comprising 55 to 6.0 fatty acids, 34 to 38% rosin acids and 6to 10% sterols. whether employed in--:crude or refined: form, tall oil will usually absorb; more than %rbyweight ofisulfur, and; in-rsome cases, up-to about 4.0%.

Although, for contemplatejdjusage as a. cutting oil base, talloils may somecases, be sulfurizedi to their maximum sulfur absorption capacity, sulfurization .to such an extent sometimesproyid'e's substances thatiindicate insolubility or otherwise unstable characteristics. in mineral oils,. Hence, and for contemplated, usage as cutting. oil. bases, itris-generally preferable tosiilfurize tancilsror absorptionthereby of uprto about. 2.5% li yight of sulfur, e g., cfrom,.about,-5 'togabout 25%,. Depending upon the; particular cuttingtoperations for which a cutting oil compositionis to beemployed, the amountv of .sulfurizedltallloillblended with a, mineral oil of lubricating grade may. "be varied over alrather wide-range, In illustration. the amount of sulfurized talloil employed-may vary from about 2 to about'j50'.% by weight, -bas.ed on the mineral oil' in providing. cutting oilzbl'ends, the lower concentrations .of the. sulfurized, base being normallyemployedfor.Iighacuttingoperations with use of increasingly higher concentrations as the severity of thev contemplatedcutting operations increases. Since. theartcisiawaresof numerousmethods for sulfurizationoi basessuch as tall oils, .it is not deemed necessary'tadescribe such: methods in, detail herein, but iorlpurposes of. illustration, a suitable method is, setlforth'i'n U; S., Patent No. 2,198,562 which; comprises1heat;- ingta-ll oil adniixedMith-Slilfllr t0 .300, to;4l10? E. for-2. to.4 hours 1 Although, for reasons.suchasaforesaid, 'iaircu has considerable -meritfor sulfurization blending of the sulfurized, product withrminera-l oils to provide cutting oil compositionswthewuse of. sulfurized talloilasia cuttingoil baseisattendantwith numerousdifficulties in cutting; opera:- tions; In one form; such;- dimculties arise from the tendency of sulfurizedltall oilcompositions to form-sludge and/or gumupon standing. enduring .use thereofincuttingoperations. In stillanother form, difficulties arise from the tendency Tonsill- .furized talloil-containing compositionsto form diificultlyrremovable, adherent-depositsron metals undergoing acutting'operation aswellas onpthe.

metal-cutting equipment, with which metals the cutting oil isincontact. 'I-hatesuch difliculties are encountered inthe normal use 0f:v sulfurized tall oil-containing cutting oils is clearlyeapparent from a prior artv disclosures,- illustrative "oi"which are disclosures such asin aforesaidUnSsBatents I Nos. 2,198,562 and 2,429,198. In'additionmo-the foregoing,- sulfurized tall oil+containing. cutting toils, have been. found to have, still another drawback inthatrthey exhibit: a decided-tendency to stain and/0r discolor netalsrwith whichithey are in contact, as, for example, the metals undergoing a cutting operation and the cutting equipment employed. In many cases, observations have shown that such staining occurs even before the cutting oil evidences breakdown by occurrence of an appreciable amount of sludge and/or formation of a difiicultly removable, adhesive deposit on the metals. Hence, and although tall oils have considerable merit for sulfurization and use as cutting oil bases, the advantages resulting from use thereof are substantially minimized, if not oftentimes outweighed, by the aforesaid drawbacks. Hence, there is a need in the art for an improved cutting oil composition, in which sulfurized tall oil is employed, that is devoid of, or inhibited against, the normal tendency of such cutting oils to exhibit the aforesaid drawbacks which, obviously, have retarded the more extensive usage of sulfurized tall oils in cutting oils. By the present invention, defined more fully hereinafter, such a need has been fulfilled by use, in a sulfurized tall oil-containing cutting oil, of certain chemical compounds that result in a novel cutting oil devoid of, or substantially inhibited against, the normal tendency of sulfurized tall oils to exhibit the aforesaid drawbacks. jj Generally speaking, and with respect to the aspect of this invention relating to compositions adaptable for use as cutting oils, such compositions comprise a blend of a mineral oil with a sulfurized tall oil and, in which blend, there is dissolved a small amount, sufficient to inhibit the sulfurized tall oil to exhibit the aforesaid drawbacks, of an oil-soluble metal salt of an ester of thiophosphoric acid. In a more specific embodiment, and particularly wherein the metal salt exhibits insolubility characteristics in the sulfurized tall oil-mineral oil blend, the invention embodies use therein of a solubilizing agent for the metal salt, particularly suitable illustrations being the metal soaps of fatty acids and the alkali and alkaline earth metal soaps of sulfonic acids.

With reference to the mineral oil component of the novel compositions, a wide range of mineral oils may be employed, the particular physical characteristics thereof being dependent upon the particular cutting operations for which the cutting oil composition is to be employed. Thus, the mineral oil component may comprise either a mineral oil or fractions thereof that possess lubrieating qualities and which may be derived from any of a variety of petroleum crudes, including the paraflinic, naphthenic and mixed crudes. In more specific aspect, the lubricating oils employed preferably have a viscosity of from about 50 to about 900 S. U. S., and still more preferably, from about 90 to about 300 S. U. S. at 100 F. and fa flash point of at least about 300 F. It should be understood, however, that although mineral oils having properties as aforesaid are particularly suitable, such properties have been set forth fas illustrating suitable characteristics from a preferred, and not limitative viewpoint, as the in f'vention'embodies use of mineral oils of lubricating quality that, though they may not possess the aforesaid properties, are nevertheless suitable for use in a cutting oil for particular cutting operations.

' In preparing the compositions of this invention that are adaptable for use as cutting oils, the mineral oil component may be a mineral oil per se, fractions thereof, or such mineral oil and ifractions that have been sulfurized so as to contain sulfur in stable solution and/or combination. By use of sulfurized oils as the mineral oil com- 4 ponent, certain advantages may be obtained, particularly in that by use of a sulfurized mineral oil for blending with sulfurized tall oil, blended compositions may be prepared that contain a higher concentration of sulfur in stable solution and/or combination than is obtainable if the mineral oil itself is not sulfurized, or for purposes of economy, certain advantages may result in using both a sulfurized mineral oil and a sulfurized tall oil in preparing the cutting oil compositions. In the use of sulfurized mineral oils, any of the methods known to the art for effecting absorption of sulfur by a mineral oil may be employed, a suitable illustration of which comprises mixing the oil with sulfur (e. g., sulfur flour) and heating the mixture with agitation at an elevated temperature such as 280 to 300 F. until the sulfur is in solution. The thus heated mixture is then allowed to cool to a normal temperature, e. g., about 70 F'., and any sulfur that may precipitate out of solution may be removed by any suitable method, e. g., filtration, to provide a mineral oil containing sulfur in stable solution and/ or combination.

The component employed in combination with the sulfurized tall oil-mineral oil blend or sulfurized tall oil-sulfurized mineral oil blend to inhibit the tendency of the sulfurized tall oil to exhibit the aforesaid drawbacks is an oil-soluble metal salt of an ester of thiophosphoric acid. In more specific illustration, such components include the oil-soluble metal salts of esters such as cetyl thiophosphate, cetyl phenyl thiophosphate, lauryl thiophosphate, octadecyl thiophosphate, dicyclohexanyl thiophosphate, oleyl thiophosphate, and the like. Especially suitable illustrations are the oil-soluble metal salts of thiophosphoric acid esters obtainable by reacting aliphatic, cycloaliphatic, or alkyl cycloaliphatic alcohols with phosphorus pentasulfide which apparently are di- (alkyl, cycloaliphatic or alkyl cycloaliphatic) thioesters of phosphoric acids. The metal salts of such esters may be prepared by any suitable means therefor known to the art, suitable examples of which include simple neutralization of the esters with suitable salt-forming bases or by double decomposition. A wide variety of saltforming radicals may be employed for the purposes of this invention but, for purposes of illustration, without intent of limitation, suitable saltforming radicals include those of metals such as zinc, barium, calcium, and the like.

In order to further illustrate the invention, the following examples are set forth. In the examples, Example I represents a composition illustrative of a commercially available cutting oil,

*containing sulfurized tall oil, which, however, is

devoid of a metal salt of a thiophosphate, and hence, is not in accordance with compositions as embodied by the present invention. The remaining examples represent compositions prepared in accordance with this invention and, by comparison of the data presented therewith with the data set forth in Example I, it is clearly evident that the compositions of this invention exhibit a marked superiority due to use therein of the metal salts of the thiophosphates in combination with tation with heating to 280 to 300 F., absorption of sulfur by the oil was efiected to the concentrations set forth in the examples.

As employed in the examples, the term sulfurized basedesignates "lnduso'il Ai as defined hereinbefore; sulfurized to a 1'5 %-"sulf ur concentration, sulfurization' thereofhaving beenefie'cted by heating Indusoil A with sulfur-flour, with agitation, at 350 F. for 2 to 3 hours.

With reference to the 'data inthe following examples,- the results set forth with-*respect -to the metal staining and adherent deposit-formcharacteristics of each com-position were-"determined by subjecting each composition to the following test: A measuredamount 0'fth'e c0m position was placed in a tin cup containing a coiled'strip of steel'in a manner wherebya'portion of the coiled strip was kept immerseddn the test oil. The test "assembly was then placed in an oven maintained at 200 F., andpat'daily intervals, the specimen was observed ror'ev-idenc'e of metal staining-and occurrence of adherent 'difiicultly-removable deposits from the meta-l suriaces in contact with the test oil composition.

Example .I

currently available cutting oil composition, ex-

hibi'ted initial metal staining within 48 hours and by the completion of 100 hoursfanadherent deposit'that was-diffieult to remove had deposited upon the metal surfaces.

Example I I In accordance with this invention, a composition was prepared comprisinga blend by weight of the followinglingredients: 92.5% 'sulfurized 4.5% sulfurized base and 3% rof Lubrizol 328, which, is understood to comprise a mineral oil solution containing "on the Ol'dGTOfEbOllt 47 to 55% by weightrof a zinc salt of .di(alkyl.-cyclohexyl) dithiophosphates. The composition of this example, when subjected to the aforesaid test, showed a marked improvement over the compositional vExample I in that initial metal staining was inhibited for about 115 hours and no formation of an'a'dherent deposit on thei'metal had occurred up to 500 hours.

'Emamplc III A composition was prepared containing ablend by weight of the following ingredients: 92 sulfurized 100 pale oil (91.2% pale oil'and 0.8% sulfur), 5.0% sulfurizingbase, 1.5 of "Lubrizol 328 and 1.5% or Petronate, the latter being a Sid-65% solution of sodium salts of mahogany acids in mineral oil. When exposed tothe conditions of the aforesaid test, initialmetal staining was inhibited for about 125 hours and no adherent deposits had occurred on the metal up to 500- hours.

Example IV A composition was prepared containing a blend by weight of the following ingredients: 93% sulfurized pale oil (92.2% pale oil and '0.'8%isulfur) 4.5% sulfurized base, and 2.5% oi"Lubrizo1338, a composition understood to comprise about 16% of a zinc salt of a di(alkylcyc1ohexyl) 'dithiophosphate and about 36% of a calcium salt of a petroleum mahogany acid dissolved in a mineral oil. When exposed to the conditions of 'theiafore- I said test, no evidence of metal stainingoccurred h n "for about 280 hours and formation "of'an ad-" 'to about 420-hours herent' =deposita-on the .metal- WaS lnH-ibitd-EEM about -450'hou-rs. l

an Example V A compositionwasiprepared containing amend by weighto'f the Stollowingiingredients:"'93'% sul furized .100 paleoil l'92i2%spale oil .and.,0i8% sulfur), 4.5% sulfurized base,-l;253% ofLubrizol 338,.and 125% of 'LPetr0n'9)te.' "When-subjected to the aforesaid test, the results obtained with respect to staining and deposition of :adherent deposits were "similar tolthose obtained in Example IV.

1 Example VI A composition wasaprepared containing ablend by weight of 932% :sul-furized 1001513351801].19212927 pale oil and 0.8% -Su1f111' );,',4:'. 5%': 'of sulfurized base, and 2 .5 of hubrizol- 54:7,"? ithe latter: being understood to .cornprise'zabont 30 -to:40-% by'wei'ght of *thebarium salt :o'f a ;di(alkylcyc1ohexyl 1 dithiophosphate dissolved 'J'IL a mineraluoil. Although such :a. composition'may be satisfactory for use inccertain cutting: "operations; such as those involving high temperatures; it has a. tendenoy to exhibit.cloudinesstand.precipitate'atnore mal temperatures broom). '.AIlence,.;to overcome such a tendency, the aforesaid :compositionrwas modified by decreasing theuamount. of Lubrizol '747 :and adding -Petronatei totprovide lthejiifollowing composition: 93% 0f :-l.O0:pale oil .(92.2% pale oil and 0.8% -su1f-ur),"a4.;5% 40f isulfurized base,--1.25% of -Lubrizol 1747 and.:. l;25% of Petronat'ei When :ithe modiiied composition was subjected-to the aforesaid test, initial-metal staining wasinhib-ited ror about 285l hours and formation of adherent deposits on the metal'zwas inhibited for about 400 hours.

'Em mple VII A composition was prepared containin -amend by weight of the followingingredients: 93% of :sulfurized .pale oil (92.2% pale oil and 0.8% sulfur), 4.5% of suliurized base, and 2.5% of "f-Aerolube. .r68,f.the. latter I being understood. to comprise a barium salt :of thiophosphoric acid esterified with :CalSO :Caaalcohols Similarlyto the-composition lset: :forthzin thei'precedingz :example, the composition :of: this rexampl'e exhibited a tendencyto developshaze'and;precipitation at normal temperature lroom) and, hence; to over- 'come sucha tendency, the:compositionawaszmodilied to the "following :i 193%. 40f .sulfurized 100.:pale oil 192.2 oil and 0,8 sulfur) ,7 4L5 sulfurized base, 1.25% .of .Aerolube 68 and 1.251% aof Petronate. .In preparing the modifiedcomposition, aconcentrate was prepared: by blending the sulfurized base, .fAerolub'e 68 and Petronate in a ratio-of 4'.5:1'.25:1.25, respectively, by weight and the concentrate was then dissolved in the sulfurized 100 pale coil .tocform .the. aforesaid-modifiedcomposition. When this composition 'sub'j ected to the aforesaid 1383178,.11'0711161331 "staining or formation *of adherent deposits shad soccurred 'upon an observation at 1,000. hours.

Example-VIII A'composition'wa-s prepared that was identical torthe modifiedcomposition of Example VIIeX- cept that sodium oleate'was substituted "for the ""Pe'tronate'. Such a composition inhibited initial metal staining for about 300 hours andno formation of adherent .d'epositswas iobserved'up 1 Although, as in the foregoing examples, specifie concentrations have been employed for the various ingredients of the compositions set forth that are highly satisfactory cutting oils, the concentrations have been employed as illustrative of specific, and not limitative, aspects of the inven: tion. As aforesaid, the invention, with respect to compositions suitable for use as cutting oils, relates to compositions comprising a mineral oil, a sulfurized tall oil, and an oil-soluble metal salt of an ester of thiophosphoric acid in an amount sufiicient to stabilize the sulfurized tall oil in the manner aforesaid, and when necessary, a olubilizing agent for the metal salts, said solubilizing agent being, preferably, an oil-soluble metal soap as illustrated by the oil soluble metal soaps of fatty acids, oil-soluble metal soaps of sulfonic acids, e. g., petroleum mahogany acids, and the like. In more specific illustration, the compositions embodied herein, comprise a mineral oil, (or sulfurized mineral oil), a sulfurized tall oil in an amount of about 2 to about 50% based upon the Weight of the mineral oil (or sulfurized min eral oil), and an oil-soluble metal salt of an ester of thiophosphoric acid in an amount sufiicient to stabilize the composition as aforesaid, the metal salt normally being employed in concentrations of from about 0.1 to about based upon the weight of the composition. In cases wherein the aforesaid metal salt indicates insolubility characteristics, the solubilizing agent should generally be employed. in a concentration on the order set forth hereinbefore for the metal salt of the thiophosphate. In still more specific .illustration are mineral oils (or sulfurized min- .eral oils) having the following concentrations of .the sulfurized tall oil and inhibitors dissolved Oil-soluble metal salt of ester of thiophosphoric acid About 0.1 to about 5.0

Although, as evidenced by the data in Examples II to VIII, it is apparent that highly satisfactory results as embodied herein are obtainedby practicing the invention in the generic manner aforesaid, particular reference is made to Example VII wherein the stabilizing component employed was Aerolube 68, a barium salt of thiophosphoric acid esterified with C6 to C8 alcohols. Although the blend, devoid of the metal soap, exhibited a tendency to haze at normal tem- "peratures, the use therein of the metal soap of -mahogany acids not only provided a clear, stable solution but, additionally, provided markedly superior results in that no metal staining nor deposition of adherent deposits had occurred after 1,000 hours of exposure in the aforedefined test. As such, and as indicated by such superior performance, a particularly preferred aspect of this invention embodies the use of barium salts of the thiophosphates in combination with an oilsoluble metal soap, and, still more preferably, barium salts of thiophosphoric acids, esterified with Ct to C8 alcohols, in combination with an oil-soluble metal salt of a petroleum mahogany acid.

In the aforesaid examples, the compositions set forth therein, with the exception of modified composition of Example VII, were prepared by blending the mineral oil with the sulfurized base and dissolving the inhibitor in the resulting blends. The modified composition of Example VII, as aforesaid, was prepared by first preparing a concentrate comprising the sulfurized tall oil and the inhibitors, the sulfurized tall oil representing the major proportion by Weight of the concentrate. Irrespective of Whether the composition embodied herein are prepared by use of a concentrate as in the modified composition of Example VII, or by blending of individual ingredients, the final compositions exhibit similar properties with respect to the action of the metal salt in inhibiting the sulfurized tall oil against its tendency to exhibit drawbacks as aforesaid. Hence, in addition to the novel cutting oils per se, the present invention also embodies as novel compositions, concentrates comprising a sulfurized tall oil in major proportion in combination with an amount of an oil-soluble metal salt of a thicphosphate suilicient to stabilize the sulfurized tall oil as aforesaid. In illustration, such concentrates may comprise, by Weight, more than 50% of suliurized tall oil, e. g., 60 to about 2 to 25% of an oil soluble metal salt of a thiophosphate, and the balance may comprise a suitable diluent and/or solvent, e. g., a mineral oil, and in cases wherein it is desired to employ an oil-soluble metal soap, the composition may suitably contain a concentration thereof of from about 2 to 20%. More specific illustrations of such concentrates include the following:

Percent by weight (a) Sulfurized tall oil 62 Zinc salt of di(alkylcyclohexyl) dithiophosphates 17-20 Mineral oil balance (2)) Sulfurized tall oil 62 Zinc salts of di(alkylcyclohexyl) dithiophosphates 8-12 Na salt of mahogany acids 12-15 Mineral oil balance (c) Sulfurized tall oil 64.0

Zinc salts of di(a1kylcyclohexy1) dithiophosphates 6.0

Ca salt of petroleum mahogany acids 14.0

Mineral oil balance .(d) Sulfurized tall oil 64.0 Zinc salts of di(alkylcyclohexyl) dithiophosphates 3.0

Na salt of mahogany acids 7.0

Mineral oil balance (e) Sulfurized tall oil 64.0

Barium salt of di alkylcyclohexyl dithiophosphates 8-12 Na salt of mahogany acids 12-15 Mineral oil balance It is apparent from the foregoing that by use of concentrates comprising the sulfurized tall oil in major proportional amount by weight blended with an oil-soluble salt of a thiophosphate, and, when desired, also containing a suitable oil-soluble metal soap, concentrates are provided that maybe employed to facilitate blending operations I in preparation of suitable cutting oils, and especially enables adjustable on-the-job preparation of such cutting oils to suit particular cutting needs that may vary as to severity of the cutting operations.

Although, and as is apparent from the foregoing description, the invention relates to compositions, adaptable for use as cutting oils, that essentially contain a mineral oil, sulfurized tall oil and. an oil-soluble metal salt of an ester of thiophosphoric acid, as well as concentrates that contain a sulfurized tall oil in combination with such a metal salt, it is within the scope of this invention to include such compositions and concentrates that may contain, in addition to the aforesaid, small amounts of other addition agents to impart certain desired properties to the compositions. In illustration, the compositions embodied herein may contain substances such as fatty oils, anti-corrosives, scenting agents, germicides, diluents, etc. However, in making use of such added ingredients the particular type and concentrations thereof employed are such as not to deleteriously alter the capacity of the metal salts of the thiophosphates from performing in desired manner, as aforedescribed, in combination with sulfurized tall oils.

Although the present invention has been described in conjunction with certain preferred embodiments thereof, those skilled in the art will readily recognize that variations and modifications are to be considered within the purview of the specification and scope of the appended claims.

I claim:

1. A composition, adaptable for use as a cutting oil, comprising a mineral oil in major amount based on the weight of said composition, an oilsoluble sulfurized tall oil in an amount sufficient to improve the lubricating qualities of said oil but having a tendency to form deposits adhesive to metals in contact therewith, and an oil-soluble metal salt of an ester of thiophosphoric acid in an amount sufiicient to inhibit said composition against formation of adherent deposits on metals in contact therewith.

2. A composition, as defined in claim 1, wherein the mineral oil is a sulfurized mineral oil.

3. A composition, as defined in claim 1, which contains, in addition, an oil-soluble solubilizing agent for said metal salt.

4. A composition, as defined in claim 3, wherein the solubilizing agent is an oil-soluble metal soap.

5. A composition, as defined in claim 1, wherein the mineral oil is a sulfurized mineral oil and which composition contains, in addition, a solubilizing agent for said metal salt.

6. A composition, as defined in claim 1, which contains the sulfurized tall oil in an amount of about 2 to about 50% based on the weight of the mineral oil.

'7. A composition, as defined in claim 1, which contains about 0.1 to about by weight of the metal salt. 1

8. A composition, as defined in claim 1, which contains the sulfurized tall oil in an amount of about 2 to about 50% based on the weightof the mineral oil and from about 0.1 to about 10 of said metal salt based on the weight of said composition.

9. A composition, as defined in claim 8, wherein the mineral oil is a sulfurized mineral oil.

10. A concentrate, adaptable for blending with a mineral oil of lubricating quality to prepare cutting oil compositions, comprising a sulfurized tall oil in major proportional amount based on the weight of said concentrate and a minor amount, sufiicient to inhibit the tendency of the sulfurized tall oil to form adherent deposits on metals in contact therewith, of an oil-soluble metal salt of a thiophosphoric acid ester.

11. A concentrate, as defined in claim 10, which. in addition, contains an oil-soluble solubilizing agent for said metal salt.

12. A concentrate, as defined in claim 11, wherein the solubilizing agent is an oil-soluble metal soap.

13. A concentrate, as defined in claim 10, which contains the sulfurized tall oil in about 60 to about based on the weight of said concentrate and the metal salt in an amount of about 2 to about 25%.

14. A concentrate, as defined in claim 13, which contains about 2 to about 20% of an oil-soluble solubilizing agent for said metal salt.

15. A composition, adapted for use as a cutting oil, comprising in major amount based on the weight of said composition a lubricating oil from the group consisting of mineral oils and sulfurized mineral oils, an oil-soluble sulfurized tall oil in an amount sufiicient to improve the lubricating qualities of said lubricating oil but having a tendency to form deposits adherent to metals in contact therewith, and an oil-soluble metal salt of an alkyl cycloaliphatic dithiophosphate in an amount sufiicient to inhibit said composition against formation of adherent deposits on metals in contact therewith.

16. A composition, as defined in claim 15, wherein the metal component of the oil-soluble metal salt is a member from the group consist ing of zinc and barium.

17. A composition, as defined in claim 15 which, in addition, contains a solubilizing agent for said metal salt, said solubilizing agent being an oilsoluble metal soap of an acid from the group consisting of fatty acids and petroleum sulfonic acids.

18. A concentrate, adapted for blending with a mineral oil of lubricating quality to prepare cutting oil compositions, comprising a sulfurized tall oil in major proportional amount based on the weight of said concentrate, an oil-soluble metal salt of an alkyl cycloaliphatic dithiophosphate in an amount sufiicient to inhibit the tendency of the sulfurized tall oil to form adherent deposits on metals in contact therewith, and a mineral oil.

19. A concentrate, as defined in claim 18, wherein the metal component of the metal salt is a member from the group consisting of zinc and barium.

20. A concentrate, as defined in claim 18, which in addition, contains a solubilizing agent for said metal salt, said solubilizing agent being an oilsoluble metal soap of an acid from the group consisting of fatty acids and petroleum sulfonic acids.

STANLEY P. WAUGH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,198,562 Pollak 'Apr. 23, 1940 2,246,415 Potter June 1'7, 1941 2,364,284 Freuler Dec. 5, 1944 2,429,198 Sudholz Oct. 14, 1947 2,502,408 Adelson Apr. 4, 1950 

15. A COMPOSITION, ADAPTED FOR USE AS A CUTTING OIL, COMPRISING IN MAJOR AMOUNT BASED ON THE WEIGHT OF SAID COMPOSITION A LUBRICATING OIL FROM THE GROUP CONSISTING OF MINERAL OILS AND SULFURIZED MINERAL OILS, AN OIL-SOLUBLE SULFURIZED TALL OIL IN AN AMOUNT SUFFICIENT TO IMPROVE THE LUBICATING QUALITIES OF SAID LUBRICATING OIL BUT HAVING A TENDENCY TO FORM DEPOSITS ADHERENT TO METALS IN CONTACT THEREWITH, AND AN OIL-SOLUBLE METAL SAID OF AN ALKYL CYCLOALIPHATIC DITHIOPHOSPHATE IN AN AMOUNT SUFFICIENT TO INHIBIT SAID COMPOSITION AGAINST FORMATION OF ADHERENT DEPOSITS ON METALS IN CONTACT THEREWITH. 